Thermostable heterocyclic polymers of aromatized bis adducts of diels-alder reaction between maleic anhydride and bisfuranic compounds

ABSTRACT

Thermostable heterocyclic polymers which are polyimides, polyimidazopyrrolones, and copolymers of an imide and imidazopyrrolonic structure are produced by the method in which aromatizated bis-adducts of the Diels-Alder reaction between maleic anhydride and bis-furanic compounds are reacted with an amino component which may be aromatic di- or tetramines as well as their mixtures.

United States Patent Berlin et al.

[ 1 Feb. 25, 1975 THERMOSTABLE HETEROCYCLIC POLYMERS OF AROMATIZED BIS ADDUCTS OF DIELS-ALDER REACTION BETWEEN MALEIC ANHYDRIDE AND BISFURANIC COMPOUNDS Inventors: Alfred Anisimovich Berlin, Lenisky prospekt, 57, kv. 9; Boris Izrailevich Liogonky, ulitsa 26 bakinskikh komissarov, 7, korpus 4, kv. 45; Boris Isaakovich Zapadinsky, prospekt Vernadskogo, 11/19, kv. 221, all of Moscow, U.S.S.R.

Filed: May 14, 1973 Appl. No.: 359,890

Related US. Application Data Continuation of Ser. No. 102,910, Dec. 30, 1970, abandoned.

US. Cl 260/47 CP, 260/30.2, 260/30.8 DS, 260/32.6 N, 260/33.4 P, 260/33.8 K, 260/45, 260/65, 260/78 TF, 260/78 UA Int. Cl. C08g 20/32 [58] Field of Search 260/47 CP, 65, 45, 78 TF, 260/78 UA, 326.3 N

References Cited v UNITED STATES PATENTS 3,179,632 4/1965 Hendrix 260/78 3,179,634 4/1965 Edwards 260/78 3,414,543 12/1968 Poufler 260/47 3,532,673 10/1970 Bell, Jr. et al. 260/78 Primary Examiner-Lester L. Lee Attorney, Agent, or Firm-Holman & Stern 57 ABSTRACT v 18 Claims, No Drawings THERMOSTABLE HETEROCYCLIC POLYMERS having high physico-chemical and mechanical charac- OF AROMATIZED BIS ADDUCTS OF tBYiStiCS- DlELS-ALDER REACTION BETWEEN MALEIC Although synthesis has been effected for producing ANHYDRIDE AND BISFURANIC COMPOUNDS a whole number of the above polymers with the use of 5 various dianhydrides of tetracarboxylic acids and This is a continuation of application Ser. No. amines, a general method of producing the polymers 102,910, filed Dec. 30, 1970, now abandoned. with predetermined properties is still unknown in the The present invention relates to production of 'thera mostable heterocyclic polymers and, more particularly, Another important property of the above-said polyhas reference to polymers formed during the reaction mers determining their industrial application is their of anhydrides of tetracarboxylic acids with an amino ability to be formed into articles. The reason is that component selected from the group consisting of arothese polymers are processed as a rule, and sometimes matic diamine, aromatic ortho, orthoor peri,-peri solely, at a stage of prepolymer. This is associated with tetramine, a mixture of aromatic diamine and aromatic the fact that the cyclizated products have a very high tetramine. softening temperature and are soluble only in concen- Further we will designate the polymers obtained durtrated mineral acids. The Fll'l polymers obtained by ing the reaction of dianhydride with aromatic diamine means of compounds, containing five-number anhyas I'll/H Pl with aromatic tetramine as l'll'l (PP), and dride cycles, after the cyclization are not soluble at all with a mixture of aromatic diand tetra-amines as and have a cross linked structure. Til 1H (P1P The processing of the above-said polymers in the pre- The polymers of the above-said classes are well polymer stage has a number of significant disadvanknown in the art, while some of these compounds, tages. Formation of-films, fibers and other articles acmethods ofproduetion thereof, modifications and assocording to this method does not allow the maximum ciated products have been patented. mechanical strength to be obtained due to the distur- The mechanism of formation of these products banee of the microstructure of the article by steam through a two-stage reaction is well known. The first evolved in the process of intermolecular cyclization. In stage is used for preparing prepolymers polyamide addition, the solvents used for the synthesis of prepolyacids soluble in aprotic solvents, which polymers will mer are usually extremely difficult for removing from further be designated asFlAK (PAK) in the case of apthe polymer prior to the cyclization. The removal of the plication of diamines or polyamide acids and as HAAK 3O solvent during the cyclization at high temperatures also (PAAK) in the case of application of tetramines; reduces the strength of the article.

i I f! HzN/Ir-A/f/z-- NH-C-flr-D-NH-fl/ During the second stage reactions of intermolecular Also known in the art is a method of making fibres cyclization take placeunder the effect of high temperafrom solutions of the above-said polymers in concentures, which leads to formation of U or HF] ru trated sulphuric acid. However, realization of this t rfmethod is associated with some difficulties in conducting this process. fi 0 An object of the present invention is to eliminate a c these disadvantages. I flAK -2nl/z0 r/ \N g Anotherf object of the invention is to provide a method 0 producing polymers having predetermined c 6 physical and chemical properties. t 11 Still another object of the invention is to develop a 0 process of synthesis of polymers capable of being pronm 0 cessed from solutions in conventional organic solvents z: N H mbtlo tarticlpsbhiaving high thermal, thermo-oxidizing and a aionsaitty. 1 fl Z1 l Yet another object of the invention is to provide a l 0 synthesis of the [1H polymers having a high thermal N u n resistance and adapted to be processed after the cyclization from solutions in sulphuric acid into fibres. rln 7 Other objects and advantages of the present invention will be apparent from the following detailed de- Also known in the art is a method of single-stage proscription of the invention. duction of, polymers when conducting the reaction in c o ing to the present invention, the abovepolyphosphoric acid. mentioned objects are attained due to synthesis of poly- The above-said polymers feature outstanding stabil- 1 mers the structure of which is described by the'followity to thermal and thermo-oxidizing destruction while ing formulae.

wherein M is a. -CH=NRN=CH, R is arylene selected g from the group consisting of eee: seem w 2O w/ 9+5 @R 4 3- 3 R' is selected from 11 group consisting of CH 0.

R is selected from the group consisting of CH ,O,SO NH; I S NH; Ar is a tetravalent aromatic radical selected from the b. arylene selected from the group consisting of group Consisting of O I l I I I .@I-}.-@@ I@ -,I8I.i

- R"' is selected from the group consisting of CH, O' n III -v v F@ A m is a number adequate for providing an intrinsic visa: cosity of the polymers in a solution of sulphuric 3 5 acid not less than 0.06 at 259C. v I The most interesting among the proposed polymers S O Selected the group commmg of are the products represented by the following formulae: P1) 0 R is arylene selected from the group consisting of 0 Pl; p 0

I 1% 00112 a N O\ I IV /v 0 IV R" is selected from the group consisting of C v m R is selected from the group H, OH, =0.

e. M is absent.

R is selected from the group consisting of an H atom. phcnyl. nziphthyl; O 0 X n is a number including 1 and 2; 0 0

Ar is arylene selected from the group consisting of m Pb I p.

The synthesis of the polymers is effected by reacting an amino component as aromatic diamine, aromatic ortho, orthoor peri-, peri-tetramine or their mixture with aromatized bis-adducts of the Diels-Alder reaction between maleic anhydride and bis-furanic compounds with an excess of one of the initial monomers not higher than at atemperature of O350C in an atmosphere of an inert gas Ar, N CO He, during a time required for obtaining an intrinsic viscosity of the solution of the above-mentioned polymers in sulphuric acid of at least 0.06 dl/gr The above bis-adducts consist of the following group of products:

where Ar stands for arylene, for example e-:ea: ace e sy:- s H:

1 W, (cg-@- where R is CH 0, 80 S, NH, where R standsfor an H atom or aryl, e.g. phenyl, naphthyl where R stands for CH O, S0 R stands for an H atom or aryl, e.g., phenyl, naphthyl.

where Ar stands for arylene, e.g.

where R stands for C Q; {it

R H, OH, O. R stands for an H atom or aryl, e.g. phenyl, naphthyl R R 0 0 k0 where R is phenyl;

The amino component for synthesis ofthe above-said polymers was composed of pand mphenylenediamines, benzidine, toluidine, anisidine, 3,3'-diaminodiphenyl, 4,4@diaminodiphenylmethane,

4,4"diaminodiphenyloxide, 4,4- diaminodiphenylsulphone, 4,4 diaminodiphenylsulphide, 4.4- diaminodiphenylamine,l ,5, 1,8- and 2,7- diaminonaphthalenes, 1,4-diaminoantracene, 3,3- diaminobenzidine, 3,3',4,4- tetraaminodiphenylmethane, 3,3 and 4 tetraminodiphenyloxide, l,2,4,5-tetraminobenzene, 1,4,5,8-tetraminenaphthalene, as well as hydrochlorides of the above-mentionedamines.

The proposed polymers were produced both by means of a two-stage process, i.e., through a stage of separating a prepolymer, and by a single-stage method.

The synthesis of the proposed polymers by the twostage method was effected in a medium of an aprotic solvent, i.e., N,N-dimethylformamide. dimethylsulphoxide, N,N-dimethylacetamide N-methylpirrolidone. having a general concentration of the initial monomers: Bis-adduct and a free base of amine of 5 to l57r at temperatures of 0 to C in a flow of an inert gas: Ar, N CO or He purified from traces of oxygen. The reaction time is varied within the range of 4 to 24 hours depending on a desirable value of the molecular weight of the prepolymer. The ratio between the monomers introduced into the reaction is quite important.

The most high-molecular products have been obtained at equimolecular ratios of the initial monomers in the solution of dimethylsulphoxide with a total concentration of the reagents of 8l0% at a temperature of 5575C.

Where bis-adducts are used which are sparingly soluble in dimethylsulphoxide, additions of inorganic salts such as LiCl, KC], NaCl, KBr, K] in an amount of 0.1-0.2 mole per litre of the reaction solution, in which case the molecular weight of the produced prepolymers is increased.

The intermolecular cyclization was effected by heating a prepolymer in the form of a powder, film, fibre, etc., to a temperature of l50-350C in a vacuum of l to mm Hg.

The production of the polymers by the single-stage method in a polyphosphoric acid was effected through slowly heating equimolecular quantities of a bis-adduct and amine hydrochlorides in an atmosphere of an inert gas: Ar, N CO He, having a total concentration of the monomers within 1 to 7% by weigh-t to a temperature of I602I0C, the reaction mixture being held at this temperature during 4 to 24 hours. An additional cyclization was effected in accordance with the known technique used for cyclization of forpolymers.

The structure of the synthesized polymers is identified by their elementary analysis and study of their infrared spectra. In the process of transfer from the FIAK orFlAAK structures to the cyclizated polymers the absorption bands characterizing the OH and NH bonds disappear at 2900 and 3400 cm, the bands of tertiary nitrogen appear at 1565 and 13 80 cm, the absorption of amide carbonyl disappears at 1665 cm, an intensive absorption of the C=O group appears at 1708 cm.- These changes have been noticed for the known I'M and FIT I structures as well as for the model compounds.

The synthesis of all the above-numbered bis-adducts was effected according to a similar scheme:

The fact that all the above-mentioned bis-adducts are produced by a simple and, what is most important, similar method, opens the way for widely varying their structure and allows one to change the structure of the polymers, thus changing their properties within a wide range.

Thus, the polymers produced by using the bisadducts of structures 1 and II with R=H are highly stable to thermooxidizing desctruction (the thermostability data are given in Table, points I, 2, 8, and I2) and this property is combined with a high ablation resistance. They are capable. of forming films at the prepolymer stage, which films after a heat treatment acquire properties characteristic of the FM and Unstructures.

These polymers after the cy'clization are soluble in concentrated mineral acids and can be processed into robenzenes, pyridine.

It should be noted that the HM and compounds are featured by all properties of polymers having a system of conjugated bonds. Poor solubility and high melting temperatures are characteristic features of such compounds and are caused by intensive intermolecular interactions. A change in the polymer structure effected due to a change in the structure of the initial compounds, in our case dianhydride. allows the intermolecular forces to be reduced. At least two methods are available for solving this problem.

The first method envisages provision of a macromolecule of the polymer with portions having an adequate thermal stability but having no systems of conjugated rr-bonds.

This method is effected in our case by means of synthesis of the polymers produced with the use of bisadducts of. the III and IV structures with R H, wherein the portions of conjugation are separated by. spiranic or ester groups. The spiranic structures are known to be the systems having an adequate thermal stability, because in this case to reduce the molecular weight of the polymer a break is required of at least two chemical bonds. At the same time, the products of such a structure having no extended rr-electron systems are soluble in a number of organic solvents. The FIFI polymers produced from the bis-adducts of the IV structure fea ture a high resistance to thermo-oxidizing destruction (see Table and points 4 and 5 and are soluble in cre- 7). The polymers are soluble in phenoles, chlorobenzene, pyridine.

Provision of steric hindrance to the effect of the intermolecular actions is another trend permitting the solubility of the polymers to be increased without significant reduction of the melting point or the temperature of decomposition of these polymers.

According to the proposed method the production of the macrochains with side substituents is obtained by introducing aryl (phenyl or naphthyl) substituents into the molecule of the initial bis-adduct of the structure, I, II, IV, V, where R phenyl, naphthyl. In order to obtain the bis-furanic compounds, 5-aryl-furfural or a-arylfuranes are employed which are produced by means of the Meerwein and Gomberg-Bachman arylation reactions respectively.

The polymers produced on the base of arylsubstituted bisaducts have a high thermal stability the lower limit of the decomposition temperature is within the range of470-500C (cf. Table, points 3, 5, l2, 10) which is only 5-l0% lower than that of respective non-substituted analogs, while being soluble in dimethylformamide, dimethylsulphoxide, and m-cresole. These polymers are capable of forming films from solutions.

In addition to the thermal stability and solubility, the proposed method makes it possible to control the otherproperties of the snythesized polymers. Thus, the polymers produced with the use of bis-adducts of the class I having R H and Ar NC H OC H p and pC H CH C H -p feature the highest ablation resistance among the said polymers, although their thermal stability is lower than that of the similar polymers having no oxygen or methylene bridges.

The polymers of a mixed imide and imidasopyrro- Ionic structure (ml 1n) have also been produced by means of condensation of the above-mentioned bisadducts with a mixture of aromatic diand tetramines. This method makes it possible to reduce the consumption of costly tetramines due to the use of rather inexpensive diamines. The amount of the diamine introduced into the reaction mixture was varied from 5 to 95% of the total charge and was determined by the requirements as to the value of the thermal stability of the copolymers obtained, because the properties are intermediate between the ["n'] and my] (cf. the Table, points l3, 14).

Further modification of the properties of the proposed polymers is obtained due to the use of the abovesaid bis-adducts in conjunction with dianhydrides of 10 racarboxylic benzenephenoltetracarboxylic and diphenyltetracarboxylic acids. This method makes it possible to vary the thermal, ablation, and electric properties of the polymers. The molar ratio of the dianhydride and the bis-adduct was varried within the range of0.0l:l to 1-:0.0l.

The polymers according to the present invention can easily be processed into films, fibres, foam plastics, moulded articles and can also. be used as a binder for laminated plastics by means of the known methods; i.e., at the prepolymer stage, The polymers produced by the single-stage method are used for producing strong fibres from solutions in a concentrated sulphuric acid, in which case all the synthesized polymers form in the sulphuric acid solutions of an adequate concentration for spinning a fibre.

The proposed polymers are advantageous in that they are adapted for processing into articles from such solvents as cresoles, substituted phenols, chlorobenzenes, and pyridines. The treatment ofa polymer, in which the processes of intermolecular cyclization is principally over, allows the mechanical strength of the article to be increased.

The proposed polymers can be used in all fields of engineering where the polymer material should meet strict relation to thermal, thermo-oxidizing, ablation and radiation stability.

The invention will be better understood by those skilled'in the art from the detailed description of some Continued 0 yew-- 0 I 0 II v 460 0 cwwgnmw '4 0 k /5 7? 52% is? i-s 575* 0 Ul-N-@N= 0 0/=A/'@W-l7f f4 ---/.'1- 465. EXAMPLE 1 polymer with obtained, the yield being equal to 82%. 5 mmoles of bis adduct of the Formula 1 (Ar Found in per cent: C, 78.98; H, 3.51; N, 13.62. Calculated for C H N O C, 78.49; H, 3.45; N, 13.08. 0.84.

R=H) and 5 mmoles of free base of 3,3',4,4'-

tetraminodiphenylmethane in 70 ml of dimethylsulphoxyde (DMSO) was heated during 18 hours in an argon atmosphere at 75C. The solution was precipitated into absolute methanol, the precipitate was filtered off, washed with methanol and dried at 60C undera vacuum of 10 mm Hg. 78% FIAAK polymer was produced.

Found in per cent: C, 66.3; H, 5.03; N, 12.94. Calculated for C H N O C, 67.6; H, 4.87; N, 12.8.

The heat treatment of the FIAAK polymer at 300C in a vacuum-0810* mm Hg leads to the fin structure. The output is equal to 84%.

Found in per cent: C, 76.9; H, 3.14; N, 14.87. Calculatedfor C H N O C, 76.5; H, 3.44; N, 14.5. The intrinsic viscosity (1 is equal to 0.34.

EXAMPLE 2 5 mmoles of tetrachlorhydrate of 3,3-

diaminobenzidine in 115 ml of polyphosphoric acid R H) and the mixture 'was gradually heated to 200C EXAMPLE 3 5 mmoles of bis-adduct of Formula I (AF lated for C H N O C,74.l l; H, 3.55; N, 8.23.

. EXAMPLE 4 5 mmoles of bis-adduet of Formula I (At R =H) and 5 mmoles of benzidine hydrochloride was treated according to the method of Example 2 to produce the FM polymer with a yield of 74%, 0.23.

Found in per cent: C. 76.3; H, 4.22; N, 8.84. Calculated for C, H ,N O C, 77.7, H, 3.73; N, 8.64.

EXAMPLE 5 Added to 5 mmoles of bis-adduct of Formula 1 (Ar R Ph) in 30 ml of DMSO during 2 hours at 65C was 4.95 mmoles of 3,3,4,4-tetraminodiphenylmethane in 20 ml of DMSO in an argon flow and the mixture was heated during 18 hours. The product was precipitated into absolute methanol, and washed, thus producing the AAK polymer, the yield being equal to 86%, [n 0.28.

Found in per cent: C, 72.6; H, 4.96; N, 9.27. Calculated for C H N O C,73.14; H, 4.8; N, 9.15.

The FlAAK product was heated 300C in a vacuum of mm Hg and thel ll lpolymer was obtained with a yield of 86%, ['q] 0.34.

Found in per cent: C, 79.8; H, 3.74; N, 10.8. Calculated for C H N O C, 77.6; H, 3.55; N, 10.6.

EXAMPLE 6 The l ll l polymer was produced from 5 mmoles of bis-adduct of Formula 1 (Ar R Ph) and 3,3-diaminobenzidine tetrachloride by the method described in Example 2, the yield being equal to 79% and [1;] 0.44.

Found in per cent: C, 79.8; H, 4.02; N, 10.34. Calculated for C H N O C,81.6; H, 3.78; N, 10.58.

EXAMPLE 7 1O mmoles of bis-adduct of Formula 11 (Ar R H) and 10 mmoles of 3,3',4,4-tetraminodipheriy1 EXAMPLE 8 10 mmoles of bis-adduct of Formula 11 (Ar R H) and 10 mmoles of 3,3-diaminobenzidine tetrachlorohydrate was treated by the method of Example 2 and was produced, the yield, 82%, [n]= 0.62.

Found, per cent: C, 81.1 H 3.34; N, 9.88. Calculated for C, H ,,N.,O C, 81.6; H, 3.4; N, 9.65.

EXAMPLE 9 By using the method of Example 2, FM was produced from 5 mmoles of bis adduct of Formula 11 (Ar R H) and 5 mmoles of n-phenylenediamine hydrochloride, the yield 78%, [1;]= 0.21. Found, per cent: C, 82,2; H, 4.16; N, 4.32. Calculated for C,, H N O C, 82.5; H, 4.3; N, 4.01.

EXAMPLE 10 2 mmoles of bis-adduct of Formula 11 (Ar CH CH;

R naphthyl) and 2 mmoles of 3,3'-diaminobenzidine hydrochloride was treated by the method of Example 2 to produce with a yield 83%, [1 0.28.

Found, per cent: C, 84.8; H, 4.34; N, 6.52. Calculated for C H N O C, 85.7; H, 4.15; N, 6.45.

EXAMPLE 11 Found, per cent: C, 69.3; H, 3.8; N, 10.4. Calculated for C H N O C, 69.7; H, 3.52; N, 9.85.

EXAMPLE 12 Fll/l was produced from 5 mmoles of bis-adduct of Formula IV (R R Ph) and 5 mmoles of 1,4-diaminonaphtha1ene by the method described in Example 2. The yield 83%, [1 ].='0.42.

Found, per cent: C, 73.9; H, 4.62; N, 3.56. Calculated for CH38N2O9I C, H, N,

EXAMPLE 13 Ell l was produced from 5 mmoles of bis-adduct of Formula IV (R R Ph) and -5 mmoles of tetrachlorhydrate of 1,2,4,5- tetraminobenzene by using the method described in Example 2. The yield 87%, [1;] 0.93.

Found, per cent: C, 74.3; H, 3.18; N, 7.68. Calculated for C4 H N O C, 74.1; H, 3.36; N, 7.52.

EXAMPLE 14 10 mmoles of bis-adduct of Formula 111 (Ar and 10 mmoles of free base of 3,3'-diaminobenzidine Found, per cent: C, 76.4; H, 3.72; N, 9.48. Calcuv lated for C;, H ,,N-,O,: C, 76.5: H, 3.35; N, 9.38.

EXAMPLE 15 By using the method described in Example 1, mm was produced from 10 mmoles of bis-adduct of Formula 111 (Ar and 10 mmoles of hydrochloric tolydine. The yield 88%, [n] 0.38.

Found, per cent: C, 75.75; H, 4.18; N, 4.95. Calculated for C H N O C, 76.1; H, 4.13; N, 4.45.

EXAMPLE 16 By using the method described in Example l,l lAAK R Ph) was added to the reaction mixture which was was produced from 2 mmoles of bis-adduct of Formula V and 2 mmoles of 3,3',4,4-tetraminodiphenyl ester. The yield 68%, [1 0.49. Found in per cent: C, 65.15; H, 6.45; N, 9.34. Calculated for C H N O C, 65.3; H, 6.12; N, 9.52.

A heat treatment ofFlAAK givesFlr l, the yield. 97% In] 0.54.

Found, per cent: C, 75.1; H, 5.03;N, 10.68. Calculated for CQ2HZQN4O3I C, H, N,

EXAMPLE 17 By using the method described in Example 2, is produced from 2 mmoles of bis-adduct of Formula V and 2 mmoles of 3,3'-diaminobenzidine hydrochloride. The yield 84%, [n] 0.72.

Found, per cent: C, 76.3; H, 5.72; N, 10.87. Calculated for C H N O C, 76.8; H, 5.6; N, 11.2.

EXAMPLE 18 By using the method described in Example 2, was produced from 2 mmoles of bis-adduct of Formula V and 2 mmolesof benzidine hydrochloride. The yield 92%, [n]= 0.64.

Found, per cent: C, 75.7; H, 5.61; N, 5.69. Calculated for C H N O C, 75.7; H, 5.92; N, 5.53.

EXAMPLE 19 0.25 mmole (0.53 g) of 3,3'-diaminobenzidine, 0.25 mmole (0.5 g) of 4,4-diaminodiphenyl ester in 23.7 ml of dimethylacetamide was heated in an argon atmosphere to a temperature of 75C. 0.5 mmole of bisadduct of Formula I (Ar then heated again during 18 hours. After that a copolymer of l lAAK and nAK was produced by the method described in Example 1, the yield 79%, [n] 0.25. After dehydration of the prepolymer, a polymer of a mixed amide and imidazopyrrolonic structure was produced, the yield 84%, [n]= 0.32.

EXAMPLE 20 0.1 mmole of tetrachlorhydrate of 3,3- diaminobenzidine, 0.4 mmole of benzidine hydrochloride and 0.5 mmole of bis-adduct of Formula 11 (Ar R H) was treated by the method described in Example 2 and a copolymer of an imide and imidazopyrrolonic structure was produced with a yield 72% and ["n] 0.18.

EXAMPLE 21 0.48 mmole of tetrachlorohydrate of 3,3-

diaminobenzidine, 0.02 mmole of benzidine hydrochlo ride, and 0.5 mmole of bis-adduct of Formula 11 (Ar R Ph) was treated by the method described in Example 2, thus producing a respective copolymer with a yield 83%, lnl= 0.42.

EXAMPLE 22 0.4 mmole of bis-adduct of Formula 1 (Ar 16 R H), 0.1 mmole of'dianhydride of 1.4.5.7-naphthalenetetracarboxylic acid, and 0.5 mmole of tetrachlorohydrate of 3,3',4,4-tetraminonaphthalene was treated by the method described in Example 2 to produce p0ly(aroylene-bis-benzimidasol). The yeild 87%, [17] 0.74.

EXAMPLE 23 0.1 mmole of bis-adduct of Formula 1 (Ar R Pb), 0.4 mmole of dianhydride of 1,4,5,8-naphthalenetetracarboxylic acid, and 0.5 mmole of tetrachlorohydrate of 3,3-diaminobenzidine was treated by the method described in Example 2 to produce a respective p0ly(aroylene-bis-benzimidasol). The yield 86%, [17] 1.2.

EXAMPLE 25 By using the method described in Example: 2. PM was produced from 5 mmoles of bis-adduct of Formula R Ph) and 5 mmoles of 3,3-diaminodiphenyl hydrochloride. The yield 91%, [1; 0.52.

Found, per cent: C, 74.0; H, 4.81; N, 3.22. Calculated for C H N o z-C, 74.2; H, 4,81; N, 3.46.

EXAMPLE 26 By using the method described in Example 1. F114 was produced from 10 mmoles of bis-adduct of For- R Ph) and 10 mmoles of free base of 4.4- diaminodiphenylmethane. The yield 74%, [1;] 0.37.

Found, per cent: C, 70.4; H, 4.83; N, 4.15. Calculated for C H;,,,N O,,: C, 71.7; H, 4.59; N, 4.28.

EXAMPLE 27 By using the method described in Example 1, HM was produced from 5 mmoles of bis-adduct of Formula ""2 R Ph) and 5 mmoles of free base of 4,4- diaminodiphenylsulphone. The yield 62%, [1 0.14. Found, per cent: C, 67.2; H, 4.05; N, 6.24; S, 7.70. Calculated for C H N O S C, 69.8; H, 3.45; N, 6.03; S. 6.89.

EXAMPLE 28 By using the method described in Example 2, HM was produced from 5 mmoles of bis-adduct of Formula R H) and 5 mmoles of 4.4'-diaminodiphenylsulphide hydrochloride. The yield 86%, [1;] 0.64.

Found, percent: C, 74.1; H, 3.58; N, 7.62; S, 4.83. Calculated for C H N O S: C, 75.0; H', 3.41; N, 7.98; S, 4.54.

, EXAMPLE 29 R111? By using the method described in Example 2, [TI and J was produced from mmoles of bis-adduct of Formula m (At: CH3

8 R' is selected from the group consisting of CH 0 and and 15 mmoles of tetrachlorhydrate of 3,3- O O diaminobenzidine The yield 78%, [1;] 1118. IV H Found, per cent: C, 73.2; H, 3.34; N, 7.96. Calcu- -c] OC- -COCH lated for C H N O :C, 74.4; H, 3.25; N, 8.26. 15

We claim:

l. Thermostable heterocyclic polymers selected from the group consisting of polyimide, polyimidazopyrrolone, and a copolymer of an imide and imidazopyrro- 5 ad lonic structure and consisting substantially of units of R' is arylene selected from'the group consisting of the general formulae:

where M stands for: or d.

a. CH N-R N=CH; R is arylene selected from the group consisting of OCH CH O 8 2\ V 2 CH R o ee oeo R" is selected from the group consisting of 33"? C243 8 and fl @eto. and

R is selected from the group consisting of H, HO

and =0: ,5 R is selected from the group consisting olan H atom. R" is selected from the group consisting ofCh 0, S0 phenyl and nnphthyl; S and NH; n is a numbcr including l and 2'.

b. arylene selected from the group consisting of Ar is arylene selected from the group consisting of 7 so I l l l I 5 l i l l v 2% w 6. A polymer characterized by the formula:

cs I Wi/ZF'Q :Xa vn J 7. A polymer consisting essentially of the formula: v aria 1 OCH; OCH; i

R is selected from the group consisting of CH 0,

S0 S and NH;

Ar is a'tetravalent aromatic radical selected from the group consisting of Q), ,W m 8. A polymer consisting essentially of the formula:

, 25 RV/// v i) 30 R"' IS selected from the group consisting of CH and O, and m is a number sufficient for provision of an 9. A method of producing thermostable heterocyclic intrinsic viscosity of the polymers in a solution of polymers selected from the group consisting of poly sulphuric acid of at least 0.06 at 25C. imide, polyimidazopyrrolone and a copolymer of imide 2- A polymer Consisting essen i lly Of the formula: and imidazopyrrolonic structure, which comprises re- Pbo wherein Ph is phenyl. acting aromatized bis-adducts of the Diels-Alder reac- Polymer consisting fissemially of fOrmlllaI 45 tion between maleic anhydride and bis-furanic com- .OPh Plio N wherein Ph is phenylv pounds with an amine component selected from the 4. A polymer consisting essentially of the formula; group consisting ol an aromatic dinminex aromatic tetwherein Ph is phenyl. ramine and a mixture of aromatic diamine and. uro

5 A polymer consisting essentially of the formula: matic tetramine, one of said initial monomers being 'selected from the group consisting of an atom H, phenyl, and naphthyl.

11. A method as claimed in claim 9, whereinone of said initial monomers is composed of bis-adducts of the Diels-Alder reaction between maleic anhydride and bis(-R-2-furyl)arylenes, where R is selected from the group consisting of an H atom, phenyl, and naphthyl.

12. A method as claimed in claim 9, wherein one said initial monomer is composed of aromatized adducts of the Diels-Alder reaction between maleic anhydride and bis-furfuryl esters of aromatic dicarboxylic acids selected from the group consisting of terephthalic, l,4,-, l,5-, 2,6-, 2,7-naphthalenedicarboxylic, and 4,4- diphenyldicarboxylic acids.

' phenonetetracarboxylic,

14. A methodas claimed in claim 9, wherein one of said initial monomers is composed of 2,2',5,5'- tetraphenyldiphenyl-3 ,3 ,4 ,4 -tetracarboxylic acid- 3,3',4,4'-dianhydride.

15. A method as claimed in claim 9, wherein the amino component consists of a compound selected from the group consisting of pand mphenylenediamines, benzidines, toluidine, anisidine, 3,3'-diaminodiphenyl,' 4,4-diaminodiphenylmethane, 4,4'-diaminodiphenyloxide,

diaminodiphenylsulphone, 4,4-

-diaminodiphenylsulphide, 4,4-diaminodiphenylamine,

1,4-, 1,5- and 2,7-diaminonaphthalenes, 1,4- diaminoanthracene, 3,3-diaminobenzidine, 3,3,4,4- tetraminodiphenylmethane, 3,3',4,4- tetraminodiphenyloxide, l,2,4,5-tetraminobenzene,

l,4,5,8-tetraminonaphthalene, and hydrochlorides of the above-mentioned amines.

16. A method as claimed in claim 9, wherein said initial monomers taken in equimolecular quantities are reacted ina medium of polyphosphoric acid at a temperature of l602lOC in an atmosphere of an inert gas selected from the group consisting of Ar, N CO and He during 4 to 24 hours to obtain a desirable intrinsic viscosity of the produced polymers, the latter being then subjected to a heat treatment at a temperature of 200 to 350C in a vacuum better than l0 mm Hg.

17. A method as claimed in claim 9, wherein added to said amino component is an equimolecular quantity of a mixture of said bis-adduct and dianhydride of tetracarboxylic acid selected from the group consisting of pyromellitic, l,4,5,8-naphthalenetetracarboxylic. 3,4.- 9, l O-perylenetetracarboxylic, 3 ,3 ',4,4 '-benzo- 3,3,4,4-diphenyloxytetracarboxylic acids, the ratio of the components in said mixture varying from 0.01:] to 1:001.

18. A polymer consisting essentially of the formula: 

1. THERMOSTABLE HETEROCYCLIC POLYMERS SELECTED FROM THE GROUP CONSISTING OF POLYAMIDE, POLYIMIDAZOPRYRROLONE, AND A COPOLYMER OF AN IMIDE AND IMIDAZOPYRROLONIC STRUCTURE AND CONSISTING SUBSTANTIALLY OF UNITS OF THE GENERAL FORMULAE:
 2. A polymer consisting essentially of the formula:
 3. A polymer consisting essentially of the formula:
 4. A polymer consisting essentially of the formula:
 5. A polymer consisting essentially of the formula:
 6. A polymer characterized by the formula:
 7. A polymer consisting essentially of the formula:
 8. A polymer consisting essentially of the formula:
 9. A method of producing thermostable heterocyclic polymers selected from the group consisting of polyimide, polyimidazopyrrolone and a copolymer of imide and imidazopyrrolonic structure, which comprises reacting aromatized bis-adducts of the Diels-Alder reaction between maleic anhydride and bis-furanic compounds with an amine component selected from the group consisting of an aromatic diamine, aromatic tetramine and a mixture of aromatic diamine and, aromatic tetramine, one of said initial monomers being taken in excess not higher than 10% at a temperature of 0*-350*C in an atmosphere of an inert gas selected from the group consisting of Ar, N2, CO2, and He, during a time period required for obtaining an intrinsic viscosity of solutions of said polymers in sulphuric acid of at least 0.06 dl/g.
 10. A method as claimed in claim 9, wherein one of said initial monomers is composed of bis-adducts of the Diels-Alder reaction between maleic anhydride and N,N'' -bis(5-R-furfurylidene)diaminoarylenes, where R is selected from the group consisting of an atom H, phenyl, and naphthyl.
 11. A method as claimed in claim 9, wherein one of said initial monomers is composed of bis-adducts of the Diels-Alder reactIon between maleic anhydride and bis(5-R-2-furyl)arylenes, where R is selected from the group consisting of an H atom, phenyl, and naphthyl.
 12. A method as claimed in claim 9, wherein one said initial monomer is composed of aromatized adducts of the Diels-Alder reaction between maleic anhydride and bis-furfuryl esters of aromatic dicarboxylic acids selected from the group consisting of terephthalic, 1,4,-, 1,5-, 2,6-, 2,7-naphthalenedicarboxylic, and 4,4''-diphenyldicarboxylic acids.
 13. A method as claimed in claim 9, wherein one of said initial monomers is composed of aromatized bis-adducts of the Diels-Alder reaction between maleic anhydride and bis-furanic compounds selected from the group consisting of 3,9-bis(5-R''-2-)-furyl)-2, 4,8,10-tetraoxaspiro(5,5)undecane, 3,11-bis(5-R''-2-)-furyl-15,-R-2-2,4,10,12-tetraoxadispiro -(5,1,5,3)hexadecane, 3,11-bis-(5-R''-furyl)-7-R-2,4,10,12-tetraoxadispiro (5,1,5,2) pentadecane, where R is selected from the group consisting of H, OH, and O; R'' is selected from the group consisting of hydrogen, phenyl, and naphthyl.
 14. A method as claimed in claim 9, wherein one of said initial monomers is composed of 2,2'',5,5''-tetraphenyldiphenyl-3,3'',4,4''-tetracarboxylic acid-3,3'',4,4''-dianhydride.
 15. A method as claimed in claim 9, wherein the amino component consists of a compound selected from the group consisting of p-and m-phenylenediamines, benzidines, toluidine, anisidine, 3,3''-diaminodiphenyl, 4,4''-diaminodiphenylmethane, 4,4''-diaminodiphenyloxide, 4,4''-diaminodiphenylsulphone, 4,4''-diaminodiphenylsulphide, 4,4''-diaminodiphenylamine, 1,4-, 1,5-and 2,7-diaminonaphthalenes, 1,4-diaminoanthracene, 3,3''-diaminobenzidine, 3,3'',4,4''-tetraminodiphenylmethane, 3,3'',4,4''-tetraminodiphenyloxide, 1,2,4,5-tetraminobenzene, 1,4,5,8-tetraminonaphthalene, and hydrochlorides of the above-mentioned amines.
 16. A method as claimed in claim 9, wherein said initial monomers taken in equimolecular quantities are reacted in a medium of polyphosphoric acid at a temperature of 160*-210*C in an atmosphere of an inert gas selected from the group consisting of Ar, N2, CO2, and He during 4 to 24 hours to obtain a desirable intrinsic viscosity of the produced polymers, the latter being then subjected to a heat treatment at a temperature of 200* to 350*C in a vacuum better than 10 1 mm Hg.
 17. A method as claimed in claim 9, wherein added to said amino component is an equimolecular quantity of a mixture of said bis-adduct and dianhydride of tetracarboxylic acid selected from the group consisting of pyromellitic, 1,4,5,8-naphthalenetetracarboxylic, 3,4,9,10-perylenetetracarboxylic, 3, 3'',4,4''-benzophenonetetracarboxylic, 3,3'',4,4''-diphenyloxytetracarboxylic acids, the ratio of the components in said mixture varying from 0.01:1 to 1:0.01.
 18. A polymer consisting essentially of the formula: 